Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
  • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
  • C08F2/40—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using retarding agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
  • C08F36/06—Butadiene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
  • C08L9/06—Copolymers with styrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

• This invention relates to a diene rubber having good processability and giving a rubber vulcanizate having high tensile strength and good abrasion resistance; and a rubber composition comprising the diene rubber.
• the invention further relates to a process for producing the above-mentioned diene rubber, and a process for producing the above-mentioned rubber composition.
• Rubber having high tensile strength and good abrasion resistance are required for a high-performance tire.
• a high-molecular-weight rubber having incorporated therein a large amount of a reinforcing agent is used for such rubber.
• a high-molecular-weight rubber has a high Mooney viscosity and poor processability, and therefore, a reinforcing agent is difficult to uniformly disperse therein by kneading.
• a high power and a substantially long time are required.
• compatibility of good processability with high tensile strength and good abrasion resistance is eagerly desired.
• JP-B Japanese Examined Patent Publication
• JP-A Japanese Unexamined Patent Publication No.
• H6-65418 a rubber composition having high tensile strength and good abrasion resistance is described, which comprises a modified low-molecular-weight aromatic vinyl-diene copolymer which has been obtained by anion living polymerization and further modification with an N-substituted amino compound, and a styrene-butadiene copolymer rubber.
• JP-A H6-200075 a rubber composition having reduced heat-build up and good abrasion resistance is described, which comprises natural rubber and/or polyisoprene rubber, a specific carbon black, and liquid polybutadiene, liquid polyisoprene or liquid styrene-butadiene copolymer rubber.
• JP-A H6-278410 a tire having a cap tread comprised of a rubber composition comprising a raw material rubber having incorporated therewith a low-molecular-weight diene polymer is described.
• This tire is said as exhibiting a reduced change of tire tread with time and having good abrasion resistance. However, its abrasion resistance is still insufficient.
• JP-B H6-86500 a process for producing a conjugated diolefin polymer is described, which has an average vinyl bond content of at least 50% by weight in the conjugated diolefin unit portion, contains 5% to 30% by weight of a fraction having a molecular weight of smaller than 100,000 and having a vinyl bond content of smaller than 50% by weight, has a Mooney viscosity (ML 1+4 ,100°C) in the range of 30 to 100, and contains at least 30% by weight of branched polymers.
• Mooney viscosity ML 1+4 ,100°C
• This conjugated diene polymer is produced by the steps of polymerizing a conjugated diolefin and an aromatic vinyl compound using an organolithium initiator in the presence of a Lewis base in a hydrocarbon solvent; adding a deactivator for deactivating the active terminals of polymer chains after the completion of polymerization; and further additional amounts of the conjugated diolefin and the aromatic vinyl compounds, the hydrocarbon solvent and the Lewis base were added to conduct polymerization.
• This production process has problems such that the polymerization is very difficult to carry out under thoroughly controlled conditions, and the production efficiency is low. Further, although the conjugated diolefin polymer is said as having high tensile strength and good abrasion resistance, the tensile strength and the abrasion resistance have not been enhanced to the sufficient extent.
• An object of the present invention is to provide a diene rubber having good processability and capable of giving a rubber vulcanizate having high tensile strength and good abrasion resistance; and further provide a rubber composition comprising the diene rubber.
• Another object of the present invention is to provide production processes by which the above-mentioned diene rubber and a rubber composition comprising the diene rubber can be industrially beneficially produced.
• a further object is to provide a diene rubber vulcanizate having high tensile strength and good abrasion resistance.
• the inventors made extensive researches and found that a diene rubber having a specific molecular weight distribution gives a rubber vulcanizate having high tensile strength and good abrasion resistance although the diene rubber exhibits good processability.
• the present invention has been completed based on this finding.
• a diene rubber (A) a process for producing the diene rubber (A), a rubber composition comprising the diene rubber (A), a process for producing the rubber composition, and a rubber vulcanizate made from the rubber composition, which are recited below.
• the diene rubber (A) of the present invention a homopolymer of a conjugated diene monomer, or a copolymer of at least two conjugated diene monomers or a copolymer of a conjugated diene monomer with other copolymerizable monomer or monomers.
• conjugated diene monomer there can be mentioned 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene and 1,3-pentadiene. Of these, 1,3-butadiene and 2-methyl-1,3-butadiene are preferable. 1,3-Butadiene is especially preferable.
• conjugated diene monomers may be used either alone or as a combination of at least two thereof.
• the amount of the conjugated diene monomer is at least 40% by weight, preferably in the range of 50% to 95% by weight and more preferably 60% to 90% by weight, based on the total weight of the monomers used for the diene rubber.
• the monomer copolymerizable with the conjugated diene monomer is not particularly limited, and includes, for example, amino group-containing vinyl monomers and aromatic vinyl monomers. Of these, aromatic vinyl monomers are preferable. As specific examples of the aromatic vinyl monomers, there can be mentioned styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, N,N-dimethylaminoethylstyrene and N,N-diethylaminoethyl- styrene. Of these, styrene is especially preferable. These copolymerizable monomers may be used either alone or as a combination of at least two thereof.
• the relative amount of the copolymerizable monomer in the copolymer is not larger than 60% by weight, preferably in the range of 5% to 50% by weight and more preferably 10% to 40% by weight, based on the total weight of the monomers used for the diene rubber.
• the content of vinyl bond (that is, the sum of 1,2-vinyl bond content and 3,4-vinyl bond content) in the conjugated diene monomer constituting the diene rubber (A) is usually at least 5% by mole, preferably in the range of 20% to 80% by mole and more preferably 30% to 70% by mole.
• the diene rubber (A) of the present invention has a weight average molecular weight (Mw) in the range of 100,000 to 3,000,000, preferably 300,000 to 2,000,000 and more preferably 600,000 to 1,500,000 as measured by gel permeation chromatography and as expressed in terms of that of polystyrene.
• Mw weight average molecular weight
• the diene rubber (A) of the present invention is characterized as having a specific molecular weight distribution. That is, the ratio of weight average molecular weight (hereinafter abbreviated to as "Mw” when appropriate) to number average molecular weight (hereinafter abbreviated to as “Mn” when appropriate) is in the range of 1.30 to 2.50, and the ratio of Mw to peak top molecular weight (hereinafter abbreviated to as "Mp” when appropriate) is in the range of 0.70 to 1.30.
• Mw weight average molecular weight
• Mn number average molecular weight
• Mp peak top molecular weight
• the ratio of Mw to Mn is preferably in the range of 1.45 to 2.40, more preferably 1.60 to 2.30. If Mw/Mn is too small, the kneadability and processability of rubber composition are poor and the abrasion resistance of a rubber vulcaniate is poor. In contrast, if Mw/Mn is too large, both of the tensile strength and abrasion resistance of a rubber vulcanizate are poor.
• the ratio of Mw to Mp is preferably in the range of 0.75 to 1.20, more preferably 0.80 to 1.10. If Mw/Mp is too small, the tensile strength of a rubber vulcanizate is low. In contrast, if Mw/Mp is too large, both of the tensile strength and the abrasion resistance of a rubber vulcaniate are poor.
• the diene rubber (A) of the present invention is produced by the following process.
• a conjugated diene monomer alone or at least two kinds of conjugated diene monomers, or a conjugated diene monomer or monomers together with other copolymerizable monomer or monomers is subjected to a living polymerization using an active organometal as a polymerization initiator in the presence of a polar compound in a hydrocarbon solvent.
• hydrocarbon solvent used in the living polymerization there can be mentioned aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; and aromatic hydrocarbons such as benzene and toluene.
• the amount of hydrocarbon solvent is not particularly limited, but is preferably such that the concentration of the monomers is in the range of 1% to 50% by weight.
• organic alkali metals are preferably used.
• the organic alkali metal includes, for example, an organolithium compound, an organosodium compound and an organopotassium compound. Nitrogen atom-containing organic alkali metals such as addition products of these organic alkali metals with an amino group-containing monomer, and organic alkali metal amides may also be used as a polymerization initiator.
• organolithium compounds such as an organo-monolithium compound and polyfunctional organolithium compound are preferable.
• An organo-monolithium compound is especially preferable.
• the amount of active organometal is appropriately chosen depending upon the molecular weight of the polymer required, but is preferably in the range of 0.1 to 30 milli-mole per 100 g of the monomer.
• polar compound there can be mentioned ether compounds, tertiary amines, alkali alkoxides and phosphine compounds. Of these, ether compounds and tertiary amines are preferable.
• the amount of polar compound is preferably in the range of 0.01 to 100 moles, more preferably 0.2 to 50 moles and especially preferably 0.4 to 30 moles, per mole of the active organometal used as a polymerization initiator. When the amount of polar compound is too small, the relative amount of vinyl bond in the conjugated diene units cannot be enhanced to a desired extent. Also when the amount of polar compound is too large, the relative amount of vinyl bond in the conjugated diene units is difficult to enhance.
• the time of addition of a polymerization stopper and the amount thereof are important. That is, a polymerization stopper is added to a polymerization mixture at a polymerization conversion in the range of 5% to 98% to deactivate 10% to 90% by mole of the active terminals present as of the initiation of polymerization (this addition is hereinafter referred to as “middle addition” when appropriate); and then, a polymerization stopper is further added after the polymerization conversion substantially reaches 100%, to completely terminate the polymerization reaction (this addition is hereinafter referred to as "final addition” when appropriate).
• the middle addition of a polymerization stopper is carried out at a time when the polymerization conversion is in the range of 5% to 98%, preferably 10% to 95% and more preferably 15% to 90%. If a polymerization stopper is added before or after the polymerization conversion falls within this range, the control of polymerization becomes difficult.
• the amount of a polymerization stopper added at the time of middle addition is such that 10% to 90% by mole, preferably 13% to 70% by mole and more preferably 15% to 50% by mole of the active terminals present as of the initiation of polymerization are deactivated. If the amount of a polymerization stopper added at the time of middle addition is too small, a resulting diene rubber has poor kneadability and processability. In contrast, if the amount of a polymerization stopper is too large, the control of polymerization becomes difficult and a substantially long time is required for the completion of polymerization.
• the addition of a polymerization stopper at a polymerization conversion of 5% to 98% can be carried out continuously or intermittently. Continuous addition is preferable.
• the polymerization is preferably carried out at a temperature in the range of -78 to 150°C in a batchwise or continuous manner.
• a polymerization stopper is continuously added while the polymerization is carried out in a continuous manner, it is preferable to adopt two separate polymerization vessels, one of which contains a polymerization mixture having a polymerization conversion of 5% to 98% for the continuous middle addition of a polymerization stopper, and the other of which contains a polymerization mixture having a polymerization conversion of substantially 100% for the final addition of a polymerization stopper.
• a polymerization stopper is intermittently added while the polymerization is carried out in a continuous manner, it is preferable to adopt a plurality of polymerization vessels so that the polymerization stopper is separately added to the vessels.
• the final addition of a polymerization stopper at a conversion of substantially at least 100% can be carried out either in the same polymerization vessel or in a separate polymerization vessel.
• the reaction temperature and reaction time for the polymerization stop reaction can be chosen from a broad range, but are preferably in the ranges of 15 to 120°C and 1 second to 10 hours, respectively.
• the polymerization stopper used for the middle addition at a polymerization conversion of 5% to 98% and the final addition at a polymerization conversion of substantially 100% can be chosen from those which are conventionally used for the polymerization of diene monomers, which include, for example, water; alcohols such as methanol and ethanol; allenes such as 1,2-butadiene; and acetylenes such as 1-butyne and 1-butene.
• the polymerization stopper further includes those which are capable of introducing a polar group to a terminal of polymer chain.
• Such polymerization stoppers are preferably compounds having a functional group containing at least one atom selected from, for example, a tin atom, a nitrogen atom, an oxygen atom and a sulfur atom.
• the polymerization stoppers include not only those which are capable of deactivating the active terminal of polymer chain to completely stop the polymerization, but also those which do not deactivate the active terminal of polymer chain and, when the above-mentioned copolymerizable monomers are copolymerized, the copolymerization proceeds at an extremely low rate.
• polymerization stopper containing a tin atom there can be mentioned trimethylmonochlorotin and triphenylmonochorotin.
• N,N-disubstituted aminoalkylacrylamide compounds and N,N-disubstituted aminoalkylmethacrylamide compounds such as N,N-dimethylaminopropylacrylamide and N,N-dimethylaminopropylmethacrylamide
• pyridyl group- containing vinyl compounds such as 4-vinylpyridine
• N-substituted cyclic amides such as N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-phenyl-2-pyrrolidone and N-methyl- ⁇ -caprolactam
• N-substituted cyclic ureas such as 1,3-dimethylethylene urea and 1,3-diethyl-2-imidazolidinone
• N-substituted aminoketones such as 4,4'-bis(dimethylamino)benzophenone
• N,N-disubstituted aminoalkylacrylamide compounds N-substituted cyclic amides, N-substituted cyclic ureas and N-substituted aminoketones are preferable. More specifically N,N-dimethylaminopropylacrylamide, N-methyl- ⁇ -caprolactam, 1,3-diethyl-2-imidazolidinone and 4,4'-bis(diethylamino)-benzophenone are especially preferable.
• polymerization stopper containing an oxygen atom there can be mentioned triphenoxychlorosilane and methyltriphenoxysilane.
• polymerization stopper containing a sulfur atom there can be mentioned bis(triethoxysilylpropyl)tetrasulfide and bis(tributoxysilylpropyl)tetrasulfide.
• the diene rubber (A) may be a terminal-modified diene rubber having a polar group at a terminal of polymer chain.
• the terminal-modified diene rubber can be produced by a method wherein the polymerization reaction is stopped with a polymerization stopper having the above-mentioned functional group for the production of the diene rubber (A).
• the terminal-modified diene rubber can also be produced by a method wherein, after the polymerization conversion reaches substantially 100% but prior to the final addition of a polymerization stopper, a monomer having a polar group is added to react with the active polymer having an active organometal bonded to a terminal of polymer chain.
• the monomer having a functional group preferably includes, for example, N,N-disubstituted aminoaromatic vinyl compounds such as N,N-dimethylaminoethylstyrene and N,N-diethylaminoethylstyrene.
• the terminal-modified diene rubber can also be produced by a method wherein the above-mentioned organoalkali metal containing a nitrogen atom is used as a polymerization initiator to introduce a polar group to a terminal for polymerization initiation.
• the polar group at a terminal of polymer chain may be substituted with another polar group.
• the polymer may be treated with a quaternarizing agent to convert the tertiary amino group to a quaternary amino group.
• the quarternarizing agent used includes, for example, an alkyl nitrate, a potassium alkylsulfate, a dialkylsulfuric acid, an arylsulfonic acid alkyl ester, an alkyl halide and a metal halide.
• the percentage of modification i.e., the ratio of the modified polymer having a polar group at a terminal of polymer chain to the total polymers is in the range of 10% to 100% by mole, based on the active terminals present as of the initiation of polymerization.
• the percentage of modification can be determined by calculating a ratio (UV/RI) of an absorption intensity (UV) as measured by an ultraviolet-visible light spectrophotometer to a differential refractive index (RI) as measured by a differential refractometer according to GPC, and calibrating according to a previously prepared calibration curve.
• a resulting rubber vulcanizate With a larger percentage of modification as obtained by terminal modification, a resulting rubber vulcanizate generally has better wet grip characteristic and more reduced heat-build up.
• the diene rubber (A) may be a coupled diene rubber, which is obtained by reacting an active polymer having a polymer chain terminal to which an active organometal has been bonded, with a coupling agent, prior to the above-mentioned final addition of a polymerization stopper.
• a coupled polymer comprised of a plurality of polymer molecules is obtained which has a structure such that the polymer chains of the polymer molecules are bonded together at the site of each polymer chain terminal having an active organometal via the coupling agent.
• the coupling agent used is not particularly limited provided that it is capable of forming a coupled diene rubber.
• tin-containing coupling agents such as tin tetrachloride; silicon-containing coupling agents such as silicon tetrachloride, tetramethoxysilane, diphenoxydichlorosilane and modified silicone; unsaturated nitrile coupling agents; ester coupling agents; halide coupling agents; phosphorus-containing coupling agents; epoxy coupling agents such as tetraglycidyl-1,3-bisaminomethylcyclohexane, epoxidized linseed oil and epoxidized polybutadiene; and isocyanate coupling agents.
• These coupling agents may be used either alone or as a combination of at least two thereof.
• the amount of coupling agent is can be appropriately chosen depending upon the required weight average molecular weight and percentage of coupling, and the reactivity of coupling agent, but is preferably in the range of 0.1 to 10 equivalent based on the active organometal.
• the coupling reaction is carried out preferably at a temperature of 0 to 150°C for 0.5 to 20 hours.
• the percentage of coupling can be appropriately chosen but is preferably in the range of 10% to 100% based on the polymer chains having an active organometal-bonded terminal.
• the percentage of coupling can be determined from peak areas as measured by differential refractometer according to GPC before and after coupling.
• the percentage of coupling is calculated from a ratio of (B)/(A) wherein (A) is an area of a peak as observed after coupling at the same position as the peak as observed before coupling, and (B) is an area of the region corresponding to higher molecular weights.
• auxiliary ingredients may be added according to the need.
• an antioxidant is preferably added to the as-obtained polymerization liquid, which includes, for example, a phenolic antioxidant, a phosphorus-containing antioxidant and a sulfur-containing antioxidant.
• the amount of antioxidant can be appropriately determined depending upon the kind of antioxidant and other factors.
• the method of recovering a diene rubber is not particularly limited.
• a direct drying method wherein a polymerization liquid is directly dried by, for example, heating whereby a solvent is removed; a method wherein a polymerization liquid is poured into a solvent incapable of dissolving a diene rubber to precipitate the diene rubber, and the precipitate is collected by filtration or other means and then dried to remove a solvent; and a method wherein high-temperature steam is blown into a polymerization liquid whereby a solvent is removed and a diene rubber is precipitated in a crumb state in water formed from steam, and then, the precipitate is collected by filtration or other means and then dried to remove moisture.
• a polymerization liquid is subjected to steam stripping to remove a solvent and form an aqueous slurry in which the diene rubber is dispersed in a crumb state therein, and then the slurry is dried.
• the procedures for steam stripping are not particularly limited and can appropriately chosen from conventional procedures.
• a dispersant or a coagulating aid is added to a polymerization liquid prior to steam stripping, or water having added therein a dispersant or a coagulating liquid is blown together with high-temperature steam into a polymerization liquid at the steam stripping.
• the dispersant used includes surface active agents such as a nonion surfactant, an anion surfactant and a cation surfactant.
• a nonion surfactant such as an ethylene oxide-propylene oxide block copolymer.
• dispersants are added preferably in an amount such that an aqueous solution having a concentration of 0.1 to 3,000 ppm is obtained.
• a water-soluble salt of a metal selected from lithium, sodium, potassium, magnesium, calcium, aluminum or tin can be used as a coagulation aid in combination with the dispersant.
• the lower limit in concentration of diene rubber crumb dispersed in water is preferably 0.1% by weight, more preferably 0.5% by weight and especially preferably 1% by weight, and the upper limit in concentration thereof is preferably not larger than 20% by weight, more not larger than 15% by weight and especially preferably 10% by weight, based on the weight of water used for steam stripping.
• a diene rubber in the form of crumb having a desired particle diameter can be obtained without any trouble for handling.
• the moisture-containing diene rubber crumb is preferably dehydrated to a moisture content in the range of 1 to 30% by weight.
• a compressional dehydrator such as a roll, a Banbury dehydrator and a screw-type extruder can be used.
• the residual moisture is removed by drying to give a dried diene rubber.
• the drying is carried out using dryers such as a screw-type extruder, a kneader-type dryer, an expander dryer and a hot-air dryer.
• the diene rubber (A) of the present invention can be used as a rubber composition, which comprises the diene rubber (A) having incorporated therein a reinforcing agent.
• the diene rubber (A) of the present invention can also be used as a rubber composition, which comprises the diene rubber (A) having incorporated therein a diene rubber (B) having a weight average molecular weight in the range of 2,000 to 90,000 as expressed in terms of that of polystyrene, and/or an oil extender for rubber, or a rubber composition, which comprises the diene rubber (A) having incorporated therein the diene rubber (B) and/or an oil extender, and futher a reinforcing agent.
• the diene rubber (B) has a weight average molecular weight (Mw) in the range of 2,000 to 90,000, preferably 5,000 to 70,000 and more preferably 10,000 to 50,000 as expressed in terms of that of polystyrene. If Mw of the diene rubber (B) is too low, a rubber vulcanizate has poor abrasion resistance. In contrast, if Mw of the diene rubber (B) is too high, the intended effect of the low molecular weight diene rubber (B) as a softening agent, such as reduction of viscosity of an unvulcanized rubber composition, and reduction of hardness of a rubber vulcanizate, cannot be obtained
• a ratio (Y/X) of 1,4-bond content (Y) in the diene rubber (B) to 1,4-bond content (X) in the diene rubber (A) is not particularly limited, but Y/X is preferably in the range of 0.2 to 1.4, more preferably 0.4 to 1.1 and especially preferably 0.6 to 1.
• a rubber composition with a too large Y/X ratio tends to give a rubber vulcanizate having low mechanical strength and poor abrasion resistance. In contrast, a rubber composition with a too small Y/X ratio is difficult to prepare.
• 1,4-bond content we mean a ratio by mole of the amount of 1,4-bonded conjugated diene monomer units to the amount of the conjugated diene monomer units in the diene rubber.
• the diene rubber (B) includes a homopolymer of a conjugated diene monomer, or a copolymer of at least two conjugated diene monomers or a copolymer of a conjugated diene monomer with other copolymerizable monomer or monomers, as similar to the case of the diene rubber (A).
• the diene rubber (B) may be a terminal-modified diene rubber, which can be produced by the same method as mentioned above for the production of the diene rubber (A).
• the process for the production of the diene rubber (B) is not particularly limited, provided that a diene rubber having the above-mentioned relatively low molecular weight can be produced.
• the same process as mentioned above for the production of the diene rubber (A) can be adopted.
• the amount of diene rubber (B) is in the range of 5 to 200 parts by weight, preferably 10 to 100 parts by weight and more preferably 30 to 60 parts by weight based on 100 parts by weight of the diene rubber (A).
• the diene rubber (B) may be used either alone or as a combination of at least two thereof.
• mineral oils and synthetic oils which are generally used for diene rubbers, can be used.
• the mineral oils include, for example, aromatic oil, naphthenic oil and paraffinic oil.
• the oil extender preferably has an aromatic carbon content (CA%) of at least 5%, more preferably at least 15%, as measured according to ASTM D3238.
• the oil extender preferably has a paraffinic carbon content (CP%) of not larger than 70%, more preferably not larger than 60% and especially preferably not larger than 50%.
• CA% aromatic carbon content
• CP% paraffinic carbon content
• the polycyclic aromatic carbon content of the oil extender is preferably smaller than 3% as measured by the method of IP 346.
• the amount of oil extender for rubber is in the range of 5 to 200 parts by weight, preferably 10 to 100 parts by weight and more preferably 30 to 60 parts by weight based on 100 parts by weight of the diene rubber (A).
• A diene rubber
• the oil extender for rubber may be used either alone or as a combination of at least two thereof.
• the amount of each of the diene rubber (B) and an oil extender is preferably at least 5 parts by weight and the sum of the diene rubber (B) and an oil extender is preferably not larger than 200 parts by weight, based on 100 parts by weight of the diene rubber (A).
• the diene rubber (B) and the oil extender can be mixed in a solid or liquid state.
• the mixing in a solid state can be effected by a procedure wherein a polymer obtained by separating from a polymerization liquid and drying the separated polymer, is mixed using a mixer such as a Banbury mixer, a roll mill or a screw extruder.
• a mixer such as a Banbury mixer, a roll mill or a screw extruder.
• the mixing in a liquid state can be effected by a procedure wherein one of the diene rubber (A) and the diene rubber (B) in a solid form is incorporated in a polymerization liquid as obtained by adding a polymerization stopper in the process for producing the other of the two rubbers, or a procedure wherein a polymerization liquid as obtained by adding a polymerization stopper in the process for producing the diene rubber (A) is incorporated with a polymerization liquid as obtained by adding a polymerization stopper in the process for producing the diene rubber (B).
• the latter procedure for mixing the two polymerization liquids as obtained by the addition of polymerization stopper is preferable.
• an oil extender for rubber there can be adopted a procedure wherein the oil extender is incorporated in a polymerization liquid as obtained by adding a polymerization stopper in the process for producing the diene rubber (A), or a procedure wherein the oil extender is incorporated in a mixture of two polymerization liquids as obtained by adding a polymerization stopper in the processes for producing the diene rubber (A) and the diene rubber (B).
• the mixing is carried in a liquid state.
• the mixing in a liquid state of a polymerization liquid as obtained by adding a polymerization stopper in the process for producing the diene rubber (A), with a polymerization liquid as obtained by adding a polymerization stopper in the process for producing the diene rubber (A), and/or an oil extender for rubber can be carried out by feeding predetermined amounts of the respective ingredients into a vessel where the ingredients are mixed together preferably using a stirrer.
• the concentration of polymer in the mixed polymer liquid is not particularly limited, but, to obtain good cohesiveness at steam stripping, the polymer concentration is usually in the range of 5 to 70% by weight, preferably 10 to 50% by weight and more preferably 10 to 30% by weight.
• a dispersant is preferably added prior to the steam stripping, for example, at the step of adding the oil extender.
• the addition of a dispersant is especially effective for a mixed liquid containing a tacky diene rubber (B)-containing liquid, to prevent undesirable sticking of polymer crumbs obtained by coagulation of the mixed liquid, and enhancing the handling characteristics.
• Diene units-containing rubber (c) other than the diene rubber (A) and the diene rubber (B) may be incorporated in the rubber composition of the present invention, provided that the rubber composition has good processability and gives a rubber vulcanizate having high tensile strength and good abrasion resisatnce.
• the diene units-containing rubber (C) there can be mentioned natural rubber, synthetic polyisoprene, polybutadiene, a styrene-butadiene copolymer, a styrene-isoprene copolymer, a styrene-isoprene-butadiene copolymer, an acrylonitrile-butadiene copolymer, a partially hydrogenated product of an acrylonitrile-butadiene copolymer, an isobutylene-isoprene copolymer and an ethylene-propylene-diene copolymer, and mixtures of these rubbers. These rubbers may be used after an oil extender is previously added therein.
• a preferable diene units-containing rubber (C) is a styrene-butadiene copolymer, prepared by emulsion polymerization or solution polymerization, and comprising 0 to 60% by weight, preferably 5 to 50% by weight and more preferably 15 to 45% by weight of styrene units.
• the amount of the diene rubber (C) is not larger than 500 parts by weight, preferably not larger than 400 parts by weight, based on 100 parts by weight of the diene rubber (A).
• the rubber composition of the present invention may further comprise a rubber having no diene units such as acrylic rubber, epichlorohydrin rubber, polyether, fluororubber, silicone rubber, ethylene-propylene rubber and urethane rubber.
• a rubber having no diene units such as acrylic rubber, epichlorohydrin rubber, polyether, fluororubber, silicone rubber, ethylene-propylene rubber and urethane rubber.
• the rubber composition of the present invention may comprise a reinforcing agent.
• Preferable reinforcing agents are silica and carbon black. Silica and carbon black may be used as a combination of the two reinforcing agents.
• the amount of the reinforcing agent is in the range of 10 to 200 parts by weight, preferably 20 to 150 parts by weight and more preferably 40 to 100 parts by weight, based on 100 parts by weight of the diene rubber (A) (when the diene rubber (A) is used alone as diene rubber) or based on 100 parts by weight of the total of the diene rubber (A) and the diene rubber (B) and/or the diene units-containing rubber (C)(when the diene rubber (B) and/or the diene units-containing rubber (C) is used in combination with the diene rubber (A)).
• the total amount of the two reinforcing agent is preferably in the range of 10 to 200 parts by weight.
• the silica used is not particularly limited, and includes, for example, dry white carbon, wet white carbon, colloidal silica, and precipitated silica which is described in JP-A S62-62838. Of these, wet white carbon predominantly comprised of hydrous silica is preferable. Carbon black having silica supported on the surface thereof, such as a carbon-silica dual phase filler, can also be used.
• the silica may be used either alone or as a combination of at least two kinds thereof.
• the nitrogen adsorption specific surface area of silica is preferably in the range of 50 to 400 m 2 /g, more preferably 100 to 220 m 2 /g and especially preferably 120 to 190 m 2 /g.
• the nitrogen adsorption specific surface area is measured by the BET method according to ASTM D3037.
• Silica preferably has an acidic pH, i.e., a pH value smaller than 7, more preferably in the range of 5 to 6.9.
• a silane coupling agent can be added in combination with silica.
• a silane coupling agent By the addition of a silane coupling agent, heat-build up of a rubber vulcanizate is more reduced and abrasion resistance thereof is more enhanced.
• the silane coupling agent is not particularly limited, and, as specific examples thereof, there can be mentioned vinyltriethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, bis(3-(triethoxysilyl)-propyl)tetrasulfide, bis(3-(triethoxysilyl)propyl)disulfide, and tetrasulfides described in JP-A H6-248116, such as ⁇ -trimethoxysilylpropyldimethylthiocarbamyltetrasulf
• the silane coupling agent may be used either alone or as a combination of at least two thereof.
• the amount of silane coupling agent is preferably in the range of 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight and especially preferably 1 to 15 parts by weight, based on 100 parts by weight of silica.
• the carbon black is not particularly limited, and includes, for example, furnace black, acetylene black, thermal black, channel black and graphite. Of these, furnace black is preferable. As specific examples of furnace black, there can be mentioned SAF, ISAF, ISAF-HS, ISAF-LS, IISAF-HS, HAF, HAF-HS, HAF-LS and FEF.
• the carbon black may be used either alone or as a combination of at least two thereof.
• the carbon black preferably has a nitrogen adsorption specific surface area (N 2 SA) in the range of 5 to 200 m 2 /g and more preferably 80 to 130 m 2 /g.
• N 2 SA nitrogen adsorption specific surface area
• the carbon black preferably has a dibutyl phthalate (DBP) absorption in the range of 5 to 300 ml/100 g and more preferably 80 to 160 ml/100g.
• DBP dibutyl phthalate
• the carbon black may be high-structure carbon black as described in JP-A H5-230290, which has a cetyltrimethylammonium bromide (CTAB) adsorption specific surface area in the range of 110 to 170 m 2 /g, and a DBP absorption (24M4DBP) in the range of 110 to 130 ml/100 g as measured after a compression under a pressure of 165 MPa is repeated four times.
• CTAB cetyltrimethylammonium bromide
• 24M4DBP DBP absorption
• the high-structure carbon black gives a rubber vulcanizate having improved abrasion resistance.
• the rubber composition of the present invention may comprise desired amounts of other conventional ingredients such as a vulcanizing agent, a vulcanization accelerator, an accelerator activator, an antioxidant, an activator, a process oil, a plasticizer, a lubricant and a filler.
• a vulcanizing agent such as a vulcanizing agent, a vulcanization accelerator, an accelerator activator, an antioxidant, an activator, a process oil, a plasticizer, a lubricant and a filler.
• sulfur such as powdery sulfur, precipitate sulfur, colloidal sulfur, insoluble sulfur and highly dispersible sulfur
• sulfur halides such as sulfur monochloride and sulfur dichloride
• organic peroxides such as dicumyl peroxide and di-tert.butyl peroxide
• quinone dioximes such as p-quinone dioxime and p,p'-dibenzoylquinone dioxime
• organic polyamine compounds such as triethylenetetramine, hexamethylenediamine carbamate and 4,4'-methylenebis-o-chloroaniline
• an alkyl phenol resin having methylol groups is preferable.
• Powdery sulfur is especially preferable.
• the sulfur may be used either alone as a combination of at least two kinds thereof.
• the amount of the vulcanizing agent is preferably in the range of 0.1 to 15 parts by weight and more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total rubber ingredients, in view of the low heat-build up, high mechanical strength and good abrasion resistance.
• sulfenamide vulcanization accelerators such as N-cyclohexyl-2-benzothiazylsulfenamide, N-t-butyl-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazolesulfenamide and N,N'-diisopropyl-2-benzothiazolesulfenamide; guanidine vulcanization accelerators such as diphenylguanidine, diorthotolylguanidine and orthotolylbiguanidine; thiourea vulcanization accelerators such as diethylthiourea; thiazole vulcanization accelerators such as 2-mercaptobenzothiazole, dibenzothiazyldisulfide and 2-mercaptobenzothiazole zinc salt; thiuram vulcanization accelerators such as tetramethylthiuram
• vulcanization accelerators may be used either alone or as a combination of at least two kinds thereof. Of these, sulfenamide vulcanization accelerators are preferable.
• the amount of the vulcanization accelerator is preferably in the range of 0.1 to 15 parts by weight and more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total rubber ingredients.
• the accelerator activator includes, for example, higher fatty acids such as stearic acid, and zinc oxide.
• zinc oxides finely divided zinc oxide particles with a particle diameter not larger than 5 ⁇ m, which have a high surface activity, are preferable, and, as specific example thereof, there can be mentioned active zinc flower having a particle diameter in the range of 0.05 to 0. 2 ⁇ m, and zinc flower having a particle diameter in the range of 0.3 to 1 ⁇ m.
• Zinc oxide which have been surface-treated with an amine dispersing agent or a wetting agent can also be used.
• the amount of the accelerator activator can be appropriately chosen, but, in the case of a higher fatty acid, its amount is preferably in the range of 0.05 to 15 parts by weight and more preferably 0.5 to 5 parts by weight. In the case of zinc oxide, its amount is preferably in the range of 0.05 to 10 parts by weight and more preferably 0.5 to 3 parts by weight.
• the process oil includes mineral oil and synthetic oil.
• mineral oil there can be usually used aromatic oil, naphthenic oil and parrafinic oil.
• ingredients may be incorporated, which include, for example, activators such as diethylene glycol, polyethylene glycol and silicone oil; fillers such as calcium carbonate, talc, clay and aluminum hydroxide; tackifiers such as a resin; and waxes.
• activators such as diethylene glycol, polyethylene glycol and silicone oil
• fillers such as calcium carbonate, talc, clay and aluminum hydroxide
• tackifiers such as a resin
• waxes waxes.
• the rubber composition of the present invention can be prepared by kneading the ingredients by the conventional procedure.
• rubbers and the ingredients other than a vulcanizing agent and a vulcanizing accelerator are kneaded together, and thereafter, a vulcanizing agent and a vulcanizing accelerator are mixed with the kneaded mixture to give a vulcanizable rubber composition.
• the kneading of rubbers and the ingredients other than a vulcanizing agent and a vulcanizing accelerator is carried out preferably at a temperature of 80 to 200°C and more preferably at 120 to 180°C, and for a time of 30 seconds to 30 minutes.
• the mixing of a vulcanizing agent and a vulcanizing accelerator is carried out after the kneaded mixture is cooled usually to a temperature of not higher than 100°C and preferably not higher than 80°C.
• the rubber composition of the present invention is put to a practical use usually as a rubber vulcanizate.
• the method for vulcanizing the rubber composition is not particularly limited and can be appropriately chosen depending upon the particular shape and size of a vulcanizate or other factors.
• a method of molding simultaneously with vulcanization can be adopted wherein a vulcanizable rubber composition is filled in a mold and then heated.
• a method of molding and then vulcanizing can also be adopted wherein a previously molded rubber article is heated for vulcanization.
• the vulcanization temperature is preferably in the range of 120 to 200°C and more preferably 140 to 180°C.
• the vulcanization time is usually in the range of about 1 to 120 minutes.
• n-butyllithium was added to treat the content until catalyst-deactivating ingredients disappeared. Thereafter 0.092 part of n-butyllithium as a catalytically active ingredient for polymerization was added to initiate polymerization at 45°C.
• Polymerization was carried out by the same procedures as described in Example 1 except that an additional monomer mixture of styrene and 1,3-butadiene, in which water had been previously added in an amount such that 30% by mole of the active terminal for polymerization was deactivated, was continuously added when 30 minutes elapsed from the initiation of polymerization, whereby a solution of polymer b was obtained. All other conditions remained the same.
• the polymerization conversion at the completion of addition of the additional monomer mixture was 76%.
• the molecular weight and structure of polymer b are shown in Table 1.
• Polymerization was carried out by the same procedures as described in Example 1 except that an additional monomer mixture, in which N-methyl- ⁇ -caprolactam instead of water had been previously added in an amount such that 23% by mole of the active terminal for polymerization was deactivated, was used with all other conditions remaining the same, whereby a solution of polymer c was obtained.
• the polymerization conversion at the completion of addition of the additional monomer mixture was 82%.
• the molecular weight and structure of polymer c are shown in Table 1.
• n-butyllithium was added to treat the content until catalyst-deactivating ingredients disappeared. Thereafter 0.092 part of n-butyllithium as a catalytically active ingredient for polymerization was added to initiate polymerization at 45°C.
• n-butyllithium was added to treat the content until catalyst-deactivating ingredients disappeared. Thereafter 0.23 part of n-butyllithium as a catalytically active ingredient for polymerization was added to initiate polymerization at 45°C.
• the first autoclave was charged with 100 parts of a monomer mixture comprised of styrene and 1, 3-butadiene at a mixing ratio of 25/75, 670 parts of cyclohexane, 0.17 part of tetramethylethylenediamine, 0.034 part of n-butyllithium, and 1,2-butadiene in an amount such that 7% by mole of the active terminal for polymerization was deactivated.
• Continuous polymerization was carried out while the monomer charge was continuously fed at a rate such that the average residence time in each autoclave was 2 hours.
• the temperatures in the first autoclave and the second autoclave were maintained at 55°C and 70°C, respectively.
• Polymerization was carried out by the same procedures as described in Production Example 1 except that the amount of tetramethylethylenediamine was changed to 6.0 parts and the amount of n-butyllthium was changed to 3.3 parts with all other conditions remaining the same, whereby a solution of polymer j was obtained.
• the molecular weight and structure of polymer j are shown in Table 1.
• Polymerization was carried out by the same procedures as described in Production Example 1 except that the amounts of styrene and 1,3-butadiene in the initial monomer charge were changed to 23 parts and 37 parts, respectively; the amounts of styrene and 1, 3-butadiene in the additional monomer mixture were changed to 327 parts and 613 parts, respectively; the amount of tetramethylethylenediamine was changed to 9.3 parts; and the amount of n-butyllithium was changed to 8.5 parts. All other conditions remained the same. Thus, a solution of polymer k was obtained. The molecular weight and structure of polymer k are shown in Table 1.
• Polymerization was carried out by the same procedures as described in Production Example 2 except that the amounts of styrene and 1,3-butadiene in the initial monomer charge were changed to 14 parts and 36 parts, respectively, and the amounts of styrene and 1,3-butadiene in the additional monomer mixture were changed to 236 parts and 714 parts, respectively, with all other conditions remaining the same. Thus, a solution of polymer l was obtained. The molecular weight and structure of polymer l are shown in Table 1.
• Example 5 In Comparative Examples 5 and 6, the above-mentioned procedures in Example 5 were repeated wherein polymer e and polymer f were used, respectively, as rubber ingredients instead of polymer a to prepare rubber compositions, with all other conditions remaining the same. The obtained rubber compositions were press-cured to prepare specimens and their properties were evaluated.
• Example 5 Comp. Ex. 5 Comp.Ex. 6 Production of rubber composition High-molecular-weight rubber a e g (parts) 100 100 100 100 Low-molecular-weight rubber (parts) - - - - - - Oil extender (parts) 37.5 37.5 37.5 Composition (parts) Carbon black 80 80 80 Zinc oxide 3 3 3 3 Stearic acid 2 2 2 Antioxidant 2 2 2 Sulfur 1.4 1.4 1.4 CBS 1.2 1.2 1.2 DPG 0.3 0.3 0.3 Physical properties Electric power for kneading 84 100 83 BIT 70 100 77 Modulus at 300% elongation 105 100 68 Abrasion resistance 136 100 102
• the rubber vulcanizate When the high-molecular-weight diene rubber is a diene rubber with too small Mw/Mp (polymer f ) , the rubber vulcanizate has poor abrasion resistance. When the high-molecular-weight diene rubber is a diene rubber with too large Mw/Mn and too large Mw/Mp (polymer g ), the rubber vulcanizate has low tensile strength and poor abrasion resistance.
• a rubber composition comprising the diene rubber (A) of the present invention, which has a specific molecular weight distribution, and the low-molecular-weight diene rubber (B) and/or an oil extender for rubber has good processability, but can give a rubber vulcanizate having high tensile strength and good abrasion resistance.
• the rubber composition of the present invention has the above-mentioned beneficial properties, and therefore, can be applied to, for example, tire parts of automobile tires such as tread, carcass, sidewall and bead, and vibration insulation materials.
• tire parts of automobile tires such as tread, carcass, sidewall and bead, and vibration insulation materials.
• the rubber composition is suitable for tire tread of high-performance tire. Further, it is suitable for materials for four-seasons tire, low-fuel-consumption tire and studless tire.

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